Oxidation dyestuffs with ascorbic acid or salts thereof for dyeing living human hair



ug. 22, 967 H, wlLMsMANN ETAL A 3,337,411

OXIDATION DYESTUFFS WITH ASCORBIC ACID OR SLTS THEREOF `FOR DYEING LIVING HUMAN HAIR Filed OC'C. 24, 1962 4 Sheets-Sheet l OXIDATION DYESTUFFS Filed OCL. 24, 1962 H. WILMSMANN ETAL DYEING LIVING HUMAN HAIR F/GZ WITH ASCORBIC ACID OR SALTS THEREOF FOR 4 Sheets-Sheet 2 c. Joa/UM SMF/7F IN VEN TORS #erna/7n /f im Maa/7,7 E 7er) Mom-062 A118 22, 1967 H. wxLMsMANN TAL 3,337,`41I

OXIDATION DYESTUFFS WITH ASCORBIC ACID OR SALT-S THEREOF FOR DYEING LIVING HUMAN HAIR Filed Oct. 24, 1962 4 Sheets-Sheet 4 United States Patent O 3 337 411 OXIDATION DYESTUFS WITH ASCORBIC ACID OR SALTS THEREOF FOR DYEING LIVING HUMAN HAIR Hermann Wilmsmann and Eugen Konrad, Darmstadt, Germany, assignors to Interpal SA., Fribourg, Switzerland Filed Oct. 24, 1962, Ser. No. 232,826 Claims priority, application Germany, Oct. 26, 1961, W 30,946 31 Claims. (Cl. 167-88) The present invention relates to the dyeing of human hair, and more particularly to the use of oxidation hair dyestuffs for the dyeing of human hair whereby improved dyeing eiiects are achieved.

It is known to add reducing substances to hair dyestutf compositions based on the use of oxidation dyestuffs in order to prevent a premature oxidation by the atmospheric oxygen. For this purpose there has been used in hair dyeing compositions hematoxylin (German Patent No. 541,404), inorganic sultes (Erdmann, Zeitschr. f. angewandte Chemie 1906, volume I, 1053), mercaptans (German Patent No. 839,991) and sodium dithionite (French Patent No. 1,052,622).

Since hematoxylin is practically inactive and sodium dithionite, because of its instability and undesired side reactions, practically unusable, the suliites and the mercaptans, particularly thioglycolic acid have found practical application in hair dyestul compositions which `are mixed with `oxidation agents shortly before use. By preventing the premature oxidation what is achieved is that in the first place the hair dyestuf does not lose its dyeing capacity prematurely, and that on the other hand prior to the mixingwith the oxidation agent a light icolored, appealing appearance is obtained which remains light colored for a relatively longer time after the application of the oxidation agent. This is important since if the dyestui mass becomes dark too quickly on the hair the control to the desired time is necessary to achieve the desired degree of dyeing is made more difficult.

With those hair dyestuffs which because of their particular chemical structure can be used as oxidation 4dyestuiis without the simultaneous use of an oxidation agent, i.e. used alone, because the `same :are oxidized by atmospheric oxygen in a short time, for example oxidation dyestuffs based on 2,4-diaminophenol (British Patent No. 802,554) the above mentioned reducing agents cannot satisfactorily be used because while the same prevent pre- `mature oxidation they simultaneously interfere with `the necessary oxidation by means of atmospheric oxygen during the coloring process, land consequently during the normal treatment time only a relatively poor depth of color is obtained, which is quite unsatisfactory. As a result, such oxidation hair dyestuffs in Igeneral are used without any reducing `agent and can only be used under Aconditions of considerable care, for example preparation and draining oli under nitrogen atmosphere.

It is accordingly a primary object of the present invention to provide hair dyestui compositions containing oxidation hair dyestuffs either of the type that can be used both with and without yan oxidation :agent (i.e. including also such oxidation hair dyestuis which can be oxidized in a relatively short time solely by latmospheric oxygen) and which :contain a reducing agent of a special type which gives particularly good results .for all types of oxidation hair dyestuts.

It is another object of the present invention to provide a reducing agent for hair dyestufr compositions which not only prevents premature oxidation from atmospheric oxygen but which also improves the depth yof dyeing as compared to hair dyestuit compositions Without the 1'e ducing agent of the present invention.

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It is another object of the present invention to provide hair dyestu ycompositions which do not require a special oxidation agent but which can be used to achieve the dyeing eliect by means of atmospheric oxygen alone and which nevertheless can be applied under ordinary conditions. i

It is still another object of the present invention to provide a method of dyeing human hair using the compositions of the invention.

Other objects and advantages of the present invention will be apparent from a further .reading of the specication and of the appended claims.

With the above and other objects in View, the present invention mainly comprises a composition for dyeing human hair, comprising an oxidation hair idyes-tuff which is adapted upon oxidation to `dye human hair, and a compound selected from the group consisting of ascorbic acid and salts thereof.

The composition may contain ran oxidizing `agent in addition, by being mixed with an oxidizing agent shortly prior to application to the hair, particularly in the case of the use of oxidation dyestutfs which require an oxidation agent in addition to atmospheric oxygen in order to achieve the `dyeing eiiect in a satisfactory period of time, or the composition, where using an oxidation dyestuft which can be rapidly dyed by means of atmospheric oxygen, maybe free of an extra oxidation agent. In either case, as will be proved below, superior dyeing eiiects are achieved by the use of ascorbic :acid or .a salt thereof in accordance with the present invention.

It should be noted that the activity of the ascorbic acid according to the present invention is 4the same with both `optical isomers thereof, namely with Vitamin C, the known L-form, 'and also with iso-ascorbic acid, the known D-form. Consequently in all of the discussion in this yapplication whenever the term ascorbic acid is used, this refers -to both optical isomers, or eithe'r one.

In addition to being applicable to the use of either isomeric form of ascorbic acid, the present invention is 'applicable to Ithe use of lall inorganic or organic lamine salts of ascorbic acid, particularly those salts the cations `of which are used to give an alkaline pH to the composition, for example sodium, potassium, ammonium, and organic amine salts such las monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, and the like.

The present invention is applicable to the use of all common oxidation hair dyestutfs that can be used for the dyeing of human hair, for example those indicated in the Colour Index, 2nd edition, 1956, volume 3, pages 35934601.

Among the most suitable oxidation hair dyestuifs for use according to the present invention are:

o-pheny-lenediamine, p-phenylenediarnine, 4-nitro-o-phenylenediamine, 4-nitro-o-phenylenediamine-dihydrochloride, maphenylenediamine, 4chlorom-phenylenediarnine, 4nitro-m-phenylenediamine, toluene-2,4-diamine,

salts of toluene2,4diamine, toluene-2,5-diamine,

5 -nitro-toluene-Z,4-diamine, toluene-2,diamine-sulfate, 2-c'hlorotoluene-3,5-diamine, 4-methoxy-m-phenylenediamine, 41methoxy-m-phenylenediaminesulfate, S-methoxy-p-phenylenediamine, 4-ethoxy-m-phenylenediamine, 4ethoxy-m-phenylenediaminefsulfate, p-pheny-lenediamine-dihydrochloride,

2-chloro-p-phenylenediamine, 2-ch1oroap-phenylenediamine-sulfate, 2ni=tro-p-phenylenediamine, 3-(p-aminoanilino -1,2propanediol, N-phenyl-p-phenylenediamine, N-phenyl-p-phenylenediamine-hydrochloride, 4,4-diaminodiphenylamine, 4,4'diaminodiphenylamine-dihydrochloride, resorcinol, 4-chlororesorcinol, pyrogallol, p-aminophenol, 2-amino-4-nitrophenol, picramic acid, m-aminophenol, paminophenol-hydrochloride, 1naphthol,

1,5 -naphthalenedio1.

It is particularly interesting to note that the ascorbic acid and salts thereof which are used as reducing agents according to the present invention in addition to giving the normal reducing agent effect of preventing prem-ature oxidation of the hair dyestuffs, quite surprisingly, as will be explained below also increase the depth of shape resulting from the use of the hair dyesltuff. Thus, with greater amounts of the ascorbic acid or salts thereof `the depth of shade is increased and darker shades are obtained.

The amount of the ascorbic acid or salt thereof for the purposes of `the :presen-t invention may be as little as 0.5%

vrby Weight of the composition including the carrier, the

oxidation dyestuff and the ascorbic acid, and the maximum amount of the ascorbic acid or salt thereof is to an extent mainly limited by the expense. In general amounts of greater than by Weight are not necessary and in order to prevent undue expense should not be used. The `most preferred amount of ascorbic acid or salt thereof is about 0.5-3% by weight.

The oxidation dyestuff may be used in any amount ordinarily used for the dyeing of hair, the amount depending of course upon the dyestuif and upon the depth of shade desired. In general amounts of about 0.1-8% by weight are used.

As indicated above the use of ascorbic acid and its salts as reducing agent according to the :present invention is equally applicable to oxidation dyestuff compositions in which the oxidation occurs solely by the atmospheric oxygen Iand to oxidation dyestuff compositions which utilize an oxidizing agent such as hydrogen peroxide, urea peroxide or sodium, potassium or ammonium perborates, percarbonates or perphospha-tes, such as sodium perborate, potassium perborate, sodium pe-rcarbonate, potassium percarbonate, ammonium perphosphate, sodium per-phosphate, etc.

With respect to the production of lighter, appealing looking hair dye compositions, the ascorbic acid and salts thereof is at rleast equal in effect to the commonly used reducing agents such as thioglycolic acid or sultes, while with respect to the obtaining of a deep coloring effect and coloring development, the ascorbic acid and salts thereof of the present invention gives far superior results.

With coloring agents to which an oxidation agent is added to cause the dyeing effect, for example p-phenylenediamine or p-toluylenediamine, with o-r Without tinting dyestuffs from the class of aromatic amines or phenols, the lightness of color with addition of ascorbic acid or its salts in the produced dyestuff composition is comparable with the lightness of color obtained by the use of thioglycolic acid additives to the dyestuff compositions, both of these additions giving a markedly lighter color than with the addition of sulfate to the composition. After mixing with oxidation agents, however, in the case of thioglycolic acid or sulflte additives the resulting dyestuff composition very rapidly darkens, so that by the time the same can be -applied to the hair it has a dark color, whereas with dyestuff compositions according to the present invention containing the addition of ascorbic acid or its salts the lightness of color is maintained for a longer time and the composition becomes d-ark much slower. This surprising effect, which will be further discussed below, is of importance for two reasons. In the rst place it is much easier for the beautician to Work with such composition, and secondly, this is an asethetic advantage because the person, for example a woman having her hair dyed does not like a dark solution to be put onto the hair, particularly where the hair is to be dyed blond, for example.

The surprising effect of the ascorbic acid and its salts of first preventing premature oxidation by atmospheric oxygen, and in spite of the retarding of the dark color in `the dyestuff mass after the addition of the oxidation -agent then actually resulting in a more intensive dyeing is apparently `due to the fact that the ascorbic acid at rst has an antioxidizing effect, and then, due to the forma-tion of dehydroascorbic acid, has a prooxidizing effect.

Immediately after the addition of the oxidizing agent the antioxidizing eifect of the ascorbic acid occurs, while the prooxidizin-g action is being built up in the mass as the dehyd-roascorbic acid is being formed.

Only ascorbic acid and its salts `gives this double action in the hair `dye compositions to which the same is added, this action not being achieved with the use of any of the reducing agents used in such compositions prior to the present invention. The antioxidative action of ascorbic acid, thioglycolic acid 'and sodium sulte all prevent prernature oxidation of the dyestuff, but only with ascorbic acid is there formed a compound (dehydroascorbic acid) which has a prooxidizing effect. In the case of dithioglycolic acid and sodium sulfate, the compounds resulting in the m-ass :by t-he use of thioglycolic acid and sodium sulte, respectively, as antioxidizing agents, the same are inactive.

The principal distinct behavior characteristics of ascorbic acid in the presence of hydrogen peroxide in hair dyestutf compositions based on the use of p-toluylenediamine as dyestuff is shown in FIGS. 1-3 of the drawings. The curves give the increase in darkness of the dyestutf after the addition of hydrogen peroxide, measured in percentual absorption with a photoelectric colorimeter (Dr. B. Lange, Model V) with an inserted green filter, in a 100 cc. ask, during a time period of 30 minutes. The dyestuff, which directly before the measurement is mixed with an equal volume of 6% hydrogen peroxide, contained in different tests normal reduction equivalent amounts of ascorbic acid, thioglycolic acid or sodium sulte. The dyestuff agents had the compositions set forth in the following examples, in which Examples 1-4 correspond to FIGS. 1-4, respectively.

Example I p-Toluylenediamine-sulfate (0.01 mol) g 2.2 Sodium hydroxide (0.02 mol) g 0.8 Ethylenediaminetetraacetic acid, disodium salt g-- 0.1 Aqueous ammonia solution, 25% cc-- 5.0 Reducing agent and water, q.s. cc-- 100 Reducing agent:

(a) Ascorbic acid (0.001 mol) g-.. 0.176 Sodium hydroxide (0.002 mol) g-.. 0.08 (b) Thioglycolic acid, (0.002 mol) g-.. 0.23 Sodium hydroxide (0.004 mol) g `0.16 (c) Sodium sulite (0.001 mol) g-- 0.126 (d) Without reducing agent Example 2 p-Toluylenediamine-sulfate (0.01 mol) g-- 2.2 m-Phenylenediamine-dihydrochloride (0.01 mol) g 1.8 Sodium hydroxide (0.04 mol) ..g 1.6 Ethylenediaminetetraacetic acid, disodium salt g 0.1 Aqueous ammonia solution, 25% cc-- 5.0 Reducing agent and water, q.s cc-- 100.0

Reducing agents as in Example 1 Prior to the addition of the hydrogen peroxide the various dyestulf solutions have the following absorption values:

1.(a) 18%; (b) 20%; (c) 18%; (d) 46%. 2.-(a) 21%; (b) 20%; (c) 72%; (d) 83%. 3.-(a) (b) 15%; (c) 21%; (d) 33%.

In the case of dyestui agents where the dyeing is achieved by air oxidation, for example compositions containing 2,4*diaminophenol as oxidation dyestuif, it is not lpossible to use the known reducing agents because dur- Ving the coloring process the oxidation by the atmospheric `coloring of the dyestuff and the dyestuff composition has only a `relatively slight dyeing power. Consequently there has been suggested for such dyeing compositions the `use of particular conditions, such as production and filling under nitrogen atmosphere in order to prevent premature oxidation.

However, if ascorbic acid is added to such dyeing agents, it is possible to carry out the production and filling in open apparatus. With respect to the dyeing result with such dyeing agents, which by air are easily oxidized, the poor oxidative action of the dehydroascorbic acid formed during the prevention of dyeing is of particular value, because with the addition of the ascorbic acid according to the present invention there is obtained a dyeing which is considerably deeper than could be previously obtained with such dyeing agents, even when the same were produced and filled under a nitrogen atmosphere.

With respect to the obtainable depth of coloring, the following sequence can be drawn up:

Maximum depth of color Ascorbic acid addition.

`Lesser depth of color Production under nitrogen.

Still lesser depth of color Production in air land rapid use.

l Unsatisfactory depth of color Addition of thioglycolic acid or sodium sulte.

This outstanding activity of .ascorbic acid (and its salts) is 4apparently due to its particularly rapid oxidizability. Because of this rapid oxidation what results is that during the time period for the dyeing of about 30 minutes the reduction agent is practically completely used up and the oxidation of the dyestul is no longer interfered with. The formed dehydroascorbic acid can then, in

Example 4 The decisive difference in the speed of oxidation is Y shown in FIG. 4.

d Aqueous reduction equivalent `amounts of ascorbic acid, thioglycolic acid and sodium sulfite are shaken in an oxygen atmosphere of accurately determined volume and the amount of oxygen used up in relationship to the time is measured. The solutions have the following compositions:

(a) Ascorbic acid (0.001 mol) g 0.176 Sodium hydroxide (0.002 mol) g 0.08 Water, q.s. cc 100.0

(b) Thioglycolic acid, (0.002 mol) g 0.23 Sodium hydroxide (0.004 mol) g 0.16

Water, q.s cc 100.0

(c) Sodium sulite (0.001 mol) g 0.126 Sodium hydroxide (0.001 mol) g 0.04 Water, q.s. cc 100.0

From FIG. 4 it is clear that the ascorbic acid is already oxidized after a few minutes, while the oxidation of thioglycolic acid and sodium sulte is not completely even after hours. By selection of suitable ascorbic acid concentration it i's possible to adjust at will the time within 30 minutes that the ascorbic acid is completely used up. The ascorbic acid concentration is preferably so chosen that the coloring mass is in contact with the hair for 5 to 10 minutes before the ascorbic acid is used up.`

The superior activity of ascorbic acid in hair dyestuif compositions is apparent from the following comparison dyeings:

Example 5 Light blond human hair is wetted with the dyeing agent, permitted to said for 30 minutes in the air, and then rinsed and dried. The dyeing agents have the following compositions:

(a) 2,4 diaminophenol dihydrochloride (0.01

mol) g 1.96 Sodium hydroxide (0.02 mol) g 0.8 Ethylenediaminetetraacetic acid, disodium salt 0.1 Aqueous ammonia solution, 25% cc 5.0 Water, q.s. cc 100.0

Production and filling under nitrogen atmosphere.

(b) As in (a), however production and lling under an atmosphere, rapid working.

(c) As in (b), however, with the addition of:

The color of these dyeing agents as well as the obtained depth of color of the hair dyed therewith is set forth in the following table:

Dyeing agent according Color of the dycstui Color oi the dyed to Example composition hair Weak yellowish- Medium blond. Deep blue violet Light blond. Weak yellowish. Dark blond. 5d.. do Llght-light blond. 5e Dark brown Do.

The following examples further illustrate hair dyestutf compositions according to the present invention:

Example 6 Gray human hair is wetted with 50 cc. of a dyeing agent which shortly before use is mixed with 50 cc. of 6% hydrogen peroxide, after 30 minutes of working time is rinsed, and then dried.

7 The dyeing agent has the following composition: Oleic acid g 35.0 Isopropyl alcohol cc 15.0 25% aqueous ammonia solution cc 18.0 Ascorbic acid g-- 0.3 p-Toluylenediamine-sulfate g 0.8 2,4diaminoanisol-sulfate ..-g 0.06 m-Aminophenol g-- 0.1 Resorcinol g 0.2 p-Aminophenol g 0.3

The dyeing agent has a weakly yellow color and it dyes the hair to a dark ash blond tone with good covering.

Example 7 20 g. of cetyl alcohol, 2 g. of sodium cetyl sulfate and g. of wool wax are heated to melting and emulsiied with 30 g. of water at 70 C. Into the still hot emulsion is introduced a hot solution of 1.1 g of p-toluylenediamine-sulfate, 0.1 g. of 2,4diaminoanisolsu1fate, 0.04 g. of m-aminophenol, 0.3 g. of resorcinol, 0.1 g. of sodium sulite, 0.5 g. of ascorbic acid as well as cc. of 25% aqueous ammonia solution in 33 cc. of water, and the mixture is stirred until cooled.

For dyeing, 25 g. of the obtained ivory white colored cream is mixed with 25 cc. of 6% hydrogen peroxide. Gray human hair is covered therewith and after 30 minutes of action time is rinsed and dried. The hair is thereby dyed to a medium brown color.

Example 8 5.0 g. of sodium lauryl sulfate, 8.0 cc. of 25% aqueous ammonia solution, 0.2 g. of disodium salt of ethylenediamine tetraacetic acid and 1.0 g. of ascorbic acid are dissolved in 60 cc. of water, and then mixed with a solution of 2.0 g. of 2,4-diaminophenol-dihydrochloride in cc. of water and diluted with water to a volume of 100 cc. This slightly yellowish solution is used to wet gray human hair, and the hair after 30 minutes of action thereon is rinsed and dried. The hair is thus thoroughly dyed to a hazelnut blond color.

Without further analysis, the foregoing will so fully reveal the gist of the present invention that others can by applying current knowledge readily adapt it for various applications without omitting features that from the 'standpoint of prior art, fairly constitute essential characteristics of the generic or specific aspects of this invention and, therefore, 'such adaptations should and are intended to be comprehended within the meaning and range of equivalence of the following claims.

What is claimed as new and desired to be secured by Letters Patent is:

1. A composition for dyeing human hair, comprising an oxidation hair dyestu adapted upon oxidation to dye human hair; an oxidizing agent; and a compound selected from the group consisting of ascorbic acid and salts thereof.

2. A composition for dyeing human hair, :comprising an alkaline carrier adapted for application to human hair; an oxidation hair dye'stuff adapted upon oxidation to dye human hair and being in an amount of about 0.1- 8% by Weight; and a compound selected from the group consisting of ascorbic acid and inorganic salts and organic amine salts thereof in an amount of about 0.05 to 10% by weight.

3. A composition for dyeing human hair, comprising an alkaline carrier adapted for application to human hair; an oxidation hair dyestuff adapted upon oxidation to dye human hair and being in an amount of about 0.1-8% by weight; a compound selected from the group consisting of ascorbic acid and inorganic salts and organic amine salts thereof in an amount of about 0.05 to 10% by weight; and an oxidizing agent in an amount suicient to oxidize said compound and said dye to thereby activate said dye and cause dyeing of human hair to which the composition is applied.

4. A composition for dyeing human hair, comprising an alkaline lcarrier adapted for application to human hair; an oxidation hair dyestui adapted upon oxidation to dye human hair and being in an amount of about 0.1-8% by weight; a compound selected from the group consisting of ascorbic acid and inorganic salts and organic amine salts thereof in an amount of about 0.05 to 10% by weight; and an oxidizing agent selected from the group consisting of hydrogen peroxide, urea peroxide and sodium, potassium and ammonium perborates, percarbonates and perphosphates in an amount suicient to oxidize said compound and said dye to thereby activate said dye and Icause dyeing of human hair to which the composition is applied.

S. A composition for dyeing human air, comprising an oxidation hair dyestuff adapted upon oxidation to dye human hair and being selected from the group consisting of o-phenylenediamine, p-phenylenediamine, 4-nitro-ophenylenediamine, 4-nitroo-phenylenediamine-dihydrochloride, m-phenylenediamine, 4-chloro-m-phenylenediamine, 4-nitro-mphenylenediamine, toluene-2,4-diamine, salts of toluene-2,4-diamine, toluene-2,5-diamine, 5-nitrotoluene-2,4-diamine, toluene-2,5diaminesulfate, 2-chlorotoluene-3,5diamine, 4-methoxy-m-phenylenediamine, 4 methoxy m phenylenediamine sulfate, 5 methoxyp-phenylenediamine, 4ethoxymphenylenediamine, 4- ethoxy m phenylenediamine sulfate, p phenylenediamine-dihydrochloride, 2chloro-p-phenylenediamine, 2- chloro-p-phenylenediamine-sulfate, 2-nitro-p-phenylenediamine, 3-(p-arninoanilino)-l,2propanediol, N-phenylp phenylenediamine, N phenyl p phenylenediaminehydrochloride, 4,4diaminodiphenylamine, 4,4diaminodiphenylamine-dihydrochloride, resorcinol, 4-chlororesorcinol, pyrogallol, p-aminophenol, 2-amino-4-nitrophenol, picramic acid, m-arninophenol, p-aminophenolhydrochlo ride, 1naphthol, 1,5-naphthalenediol; and a compound selected from the group consisting of ascorbic acid and salts thereof.

6. A composition for dyeing human hair, comprising an alkaline carrier adapted for application to human hair; an oxidation hair dyestuff adapted upon oxidation to dye human hair and being selected from the group consisting of o-phenylenediamine, p-phenylenediamine, 4nitroo phenylenediamine, 4-ntro-o-phenylenediamine-dihydro chloride, m-phenylenediamine, 4-chloro-m-phenylenedamine, 4-nitroam-phenylenediamine, toluene-2,4-diamine, salts of toluene-2,4-diamine, toluene-2,5-diamine, 5-nitrotoluene-2,4-diamine, toluene-2,5-diamine-sulfate, 2chlo rotoluene3,5diamine, 4-methoxy-m-phenylenediamine, 4 methoxy m phenylenediamine sulfate, 5 methoxyp-phenylenediamine, 4-ethoxy-m-phenylenediamine, 4 ethoxy-m-phenylenediamine-sulfate, p-phenylenediaminedihydroc'hloride, 2-chloropphenylenediamine, 2-chlorop-phenylenediamine-sulfate, 2-nitro-pphenylenediamine, 3-(p-aminoanilino 1,2propanediol, N-phenyl-p-phenylenediarnine, N-phenyl-p-phenylenediamine-hydrochloride, 4,4diaminodiphenyla.mine, 4,4diaminodiphenylamine dihydrochloride, resorcinol, 4-chlororesorcinol, pyrogallol, p-aminophenol, 2-amino-4-nitrophenol, picramic acid, m-aminophenol, p-aminophenol-hydrochloride, 1-naphthol, 1,5-naphthalenediol and being in an amount Sul-licient to dye the hair to which the composition is applied; and a compound selected from the group consisting of ascorbic acid and inorganic salts and organic amine salts thereof in an amount of about 0.05 to 10% by weight.

7. A composition for dyeing human hair, comprising an alkaline carrier adapted for application to human hair; an oxidation hair dyestuff adapted upon oxidation to dye human hair and being selected from the group consisting of o-phenylenediamine, p-phenylenediamine, 4-nitro-ophenylenediamine, 4-nitro-o-phenylenediamine-dihydro chloride, m-phenylenediamine, 4-chloro-m-phenylenediamine, 4-nitro-m-phenylenediamine, toluene-2,4-diamine, salts of toluene-2,4-diamine, toluene-2,5-diamine, 5- nitrotoluene-2,4diamine, toluene-2,5diamine-sulfate, 2-

chlorotoluene 3,5 diamine, 4 methoxy in phenylenediamine, 4methoxym-phenylenediamine-sulfate, 5- methoxy-p-phenylenediamine, 4-ethoxy-m-phenylenediamine, 4-ethoxy-m-phenylenediamine-sulfate, p-phenylenediamine-dihydrochloride, 2-chloro-p-phenylenediamine, 2- chloro-p-phenylenediamine-sulfate, 2-nitro-p-phenylenediamine, 3-(p-aminoanilino)1,2 propanediol, N-phenylp phenylenediamine, N phenylp phenylenediaminehydrochloride, 4,4diaminodiphenylamine, 4,4'diamino diphenylamine-dihydrochloride, resorcinol, 4-chlororesorcinol, pyrogallol, p-aminophenol, 2-amino-4-nitrophenol, picramic acid, m-aminophenol, p-aminophenol-hydrochlo ride, 1naphthol, 1,5-naphthalenediol and being in an amount of about Utl-8% by Weight; a compound selected from the group consisting of ascorbic acid and inorganic Salts and organic amine salts thereof in an amount of about 0.05 to 10% by Weight; and an oxidizing agent in an amount sufficient to oxidize said compound and said dye to thereby activate said dye and cause dyeing of human hair to which the composition is applied.

8. A composition for dyeing human hair, comprising an alkaline carrier adapted for application to human hair; an oxidation ha-ir dyestutf adapted upon voxidation to dye human hair and being present in -an amount of about 0.1-8% by weight, said oxidation hair dyestuif being selected from the group consisting of o-phenylenediamine, p phenylenediamine, 4 nitro o phenylenediamine, 4- nitro o phenylenediamine dihydrochloride, m phenylenedi-amine, 4 chloro m phenylenediami-ne, 4 nitrom phenylenediamine, toluene 2,4 diamine, salts of toluene 2,4 diamine, toluene 2, diamine, 5 nitrotoluene 2,4 diamine, toluene 2,5 diamine sulfate, 2- chlorotoluene 3,5 diamine, 4 methoxy m phenylenediamine, 4 methoxy m phenylenediamine sulfate, 5 methoxy p phenylenediamine, 4 ethoxym phenylenediamine, 4 ethoxy m phenylenediamine sulfate, p phenylenediamine dihydrochloride, 2 chloro p phenylenediamine, 2 chloro p phenylenediamine sulfate, 2 nitro p phenylenediamine, 3- (p aminoanilino) 1,2 propanediol, N phenyl pphenylenediamine, N phenyl p phenylenediamine hydrochloride, 4,4 diaminodiphenylamine, 4,4 diaminodiphenylamine dihydrochloride, `resorcinol, 4 chlororesorcinol, pyrogallol, p aminophenol, 2 amino 4- nitrophenol, picramic acid, m aminophenol, p aminophenol hydrochloride, l naphthol and 1,5 naphthalenediol; a compound selected from the group consisting 4of ascorbic acid and inorganic salts and organic Iamine salts thereof in an amount of about 0.05 to by weight; and an oxidizing agent selected from the group consisting `of hydrogen peroxide, urea peroxide and sodium, potassium and ammonium perborates, percarbonates and perphosphates in an amount sufiicient to oxidize said compound and said dye to thereby activate said dye `and cause dyeing of human hair to which the composition is applied.

9. The method of dyeing human hair, Which comprises applying to human hair to be dyed in an alkaline medium a compound selected from the gnoup consisting of ascorbic acid and inorganic salts and organic amine salts thereof, and an oxidation hai-r dyestuif adapted upon oxidation by atmospheric oxygen to dye the hair.

10. The method of dyeing human hair, which comprises applying to human hair to be dyed in an `alkaline medium a compound selected from the group consisting of ascorbic acid and inorganic salts and organic amine salts thereof, an oxidation hair dyestuff adapted to be oxidized by an oxidizing agen-t and upon oxidation to dye the hair, and an oxidizing agent for said oxidation hai-r dyestuif.

11. The method of dyeing human hair, which comprises applying to human hair to be dyed an alkaline carrier containing about 0.05 to 10% by Weight of a compound selected from the group consisting of ascorbic acid and inorganic salts and organic amine salts thereof, and also containing an oxidation hair dyestuff adapted upon oxidation by atmospheric oxygen to dye the hair.

applying to human hair lto be dyed an alkaline carrier containing about 0.05% to 10% by weight of a compound selected from the group consisting of ascorbic acid and inorganic salts and organic amine salts thereof, and also containing about 0.1-8% by Weight of an oxidation hair dyestuff adapted upon oxidation by atmospheric oxygen to dye the hair.

13. The method of dyeing human hair, which comprises applying to human hair to be dyed an alkaline carrier containing about 0.05% to 10% by weight of a compound selected from the group consisting of ascorbic acid and inorganic salts and organic amine salts thereof, and also containing an oxidation hair dyestuif adapted to be oxidized by an oxidizing agent and upon oxidation to dye the hair, and oxidizing agent for said oxidation hair dyestuff.

14. The method of :dyeing human hair, which comprises lapplying to human hair to be dyed an alkaline carrier containing about 0.05% to 10% by Weight of a compound selected from the group consisting of ascorbic acid and inorganic salts and organic amine salts thereof, and also containing an oxidation hair dyestuff adapted to be oxidized by an oxidizing agent and upon oxidation to dye the hair, and an oxidizing agent fo-r said Oxidation hair dyestuff selected from the group consisting of hydrogen peroxide, urea peroxide and sodium, potassium and ammonium perborates, percarbonates and perphosphates.

15. The method of dyeing human hair, which comprises applying to huma-n hair to be dyed in an `alkaline medium a compound selected from the group consist-ing of ascorbic acid and inorganic salts and organic amine salts thereof, and an oxidation hair dyestuif adapted upon oxidation by atmospheric oxygen to dye the hair and being selected from the group consist-ing of o-phenylenediamine, pphenylenediamine, 4-nitro o phenylenediamine, 4-nitroo phenylenediamine dihydrochloride, m phenylenediamine, 4 chloro rn phenylenediamine, 4 nitro mphenylenediamine, toluene 2,4 diamine, salts of toluene- 2,4 diamine, toluene 2,5 diamine, 5 nitro toluene- 2,4 diamine, toluene 2,5 diamine sulfate, 2 chlorotoluene 3,5 diamine, 4 methoxy m phenylenediamine, 4 methoxy m phenylenediamine sulfate, 5- methoxy p phenylenediamine, 4 ethoxy m phenylenediamine, 4 ethoxy m phenyienedi'arnine sulfate, p phenylenediamine dihydrochloride, 2 chloro pphenylenediamine, 2 chloro p phenylenediamine sulfate, 2nitro p phenylenediamine, 3 (p aminoanilino) 1,2 propanediol, N phenyl p phenylenediamine, N- phenyl p phenylenediamine hydrochloride, 4,4 di- 'aminodiphenylamina 4,4 diaminodiphenylamine dihydroch-loride, resorcinol, 4 chlororesorcinol, pyrogallol, p aminophenol, 2 amino 4 nitrophenol, picramic acid, m aminophenol, p aminophenol hydrochloride, l-naphthol, 1,5-naphthalenediol.

16. The method of dyeing human hair, Which comprises applying to human hair to be dyed an alkaline carrier containing about 0.05% to 10% by Weight of a compound selected from the group consisting of ascorbic acid and inorganic salts and organic amine salts thereof, and also containing an oxidation hair dyestuff adapted to be oxidized by an oxidizing agent and upon oxidation to dye the hair and being selected from the group consisting of o-phenylenediamine, p-phenylenediamine, 4- nitro-o-phenylenediamine, 4 nitro-o-phenylenediaminedihydrochloride, m phenylenediamine, 4 chloro mphenylenediamine, 4 nitro-m-phenylenediamine, toluene- 2,4-diamine, salts of toluene-2,4-diamine, toluene-2,5- Y

diamine, 5-nitro-toluene-2,4diamine, toluene 2,5 diamine-sulfate, 2-chlorotoluene-3,5-diamine, 4-methoxym-phenylenediamine, 4-methoxy m phenylenediaminesulfate, 5 methoxy p phenylenediamine, 4 ethoxy-mphenylenediamine, 4ethoxy-m-phenylenediamine-sulfate, p-phenylenediamine-dihydrochloride, 2 chloro-p-phenylenediamine, 2chloro-p-phenylenediamine-sulfate, Z-ntropphenylenediamine, 3- (p-aminoanilino) -l,2propanediol, N-phenyl-p-phenylenediamine, N phenyl-p-phenylenediamine-hydrochloride, 4,4diaminodiphenylamine, 4,4'di aminodiphenylamine-dihydrochloride, resorcinol, 4-chloro-resorcinol, pyrogallol, p-aminophenol, 2iamino4nitro phenol, picramic acid, m-aminophenol, p-aminophenol-hydrochloride, 1-naphthol, 1,5 naphthalenediol, and an oxidizing agent for said oxidation hair dyestuff selected from the g-roup consisting of hydrogen peroxide, urea peroxide and sodium, potassium and ammonium perborates, percarbonates and perphosphates.

17. A composition for dyeing human hair comprising p-phenylenediamine and a compound selected from the g-roup consisting of ascorbic acid and inorganic salts and organic amine salts thereof.

18. A composition for dyeing human hair comprising p-toluenediamine and a compound selected from the group consisting of ascorbic acid and inorganic salts and organic amine salts thereof.

19. A composition for dyeing human hair comprising 5-methoxy-p-phenylenediamine and a compound selected from the group consisting of ascorbic acid and inorganic salts and organic amine salts thereof.

20. The method of dyeing human hair, which comprises ap-plying to human hair to be dyed in an alkaline medium an eiective amount of a compound selected from the group consisting of ascorbic acid and inorganic salts and organic amine salts thereof, and an effective amount of an oxidation hair dyestuff selected from the group consisting of p-phenylenediamine, p-toluenediamine and 5- methoxy-p-phenylenediamine.

21. A composition for dyeing human hair, comprising in an alkaline medium `an oxidation hair dyestuff adapted upon oxidation to dye human hair; and the sodium salt of ascorbic acid.

22. A composition for dyeing human hair, compris` ing in an alkaline medium an oxidation hair dyestui adapted upon oxidation to dye human hair; and the potassium salt of ascorbic acid.

23. A composition for dyeing human hair, comprising in an alkaline medium an oxidation hair dyestui adapted upon oxidation to dye human hair; and the ammonium salt of ascorbic acid.

24. A composition for dyeing human hair, comprising in an alkaline medium an oxidation hair dyestui adaptedupon oxidation to dye human hair; and an organic amine salt of ascorbic acid.

25. A method for dyeing living human hair comprising applying to the human air an oxidation hair dyestut and a compound selected from the group consisting of ascorbic acid and salts thereof.

26. A composition for dyeing human hair comprising an oxidation hair dyestuff; and a compound selected from the group consisting of ascorbic acid and salts thereof.

27. A composition as defined in claim 26, wherein said salt is selected from the group consisting of inorganic salts and organic amine salts of ascorbic acid.

28. A composition as defined in claim 26, wherein said oxidation hair dyestuff and said compound are incorporated in an alkaline medium.

29. A composition as dened in claim 28, wherein said salt is selected from the group consisting of inorganic salts and organic amine salts of ascorbic acid.

30. A method as dened in claim 25, wherein said compound and said oxidation hair dyestui are applied in an alkaline medium.

31. A method as defined in claim 25, wherein said salt is selected from the group consisting or inorganic salts and organic amine salts of ascorbic acid.

References Cited UNITED STATES PATENTS 2,375,250 5/ 1945 Riemenschneider 167-81 XR 2,376,884 5/1945 Schwen et al. 167--90 2,934,396 4/1960 Charle 167-88 XR OTHER REFERENCES ALBERT T. MEYERS, Primary Examiner. F. CACCIAPAGLIA, JR., LEWIS GOTTS, Examiners.

I. S. LEVITT, V. C. CLARKE, Assistant Examiners.

& Aromatics 63(3), 

25. A METHOD FOR DYEING LIVING HUMAN HAIR COMPRISING APPLYING TO THE HUMAN AIR AN OXIDATION HAIR DYESTUFF AND A COMPOUND SELECTD FROM THE GROUP CONSISTING OF ASCORBIC ACID AND SALTS THEREOF. 